CN106635002A - Sm<3+>-doped BiOCl orange red fluorescent powder and preparation method thereof - Google Patents
Sm<3+>-doped BiOCl orange red fluorescent powder and preparation method thereof Download PDFInfo
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- CN106635002A CN106635002A CN201611264878.1A CN201611264878A CN106635002A CN 106635002 A CN106635002 A CN 106635002A CN 201611264878 A CN201611264878 A CN 201611264878A CN 106635002 A CN106635002 A CN 106635002A
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
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Abstract
The invention discloses Sm<3+>-doped BiOCl orange red fluorescent powder and a preparation method thereof. The preparation method comprises the following steps: with Sm2O3 and Bi2O3 as raw materials, weighing the raw materials at the chemical stoichiometric ratio of the chemical formula BiOCl:xSm<3+>, wherein x=0.010-0.030; performing centrifugal separation on white sediment, conducting repeated washing with deionized water to remove Cl<-> in the white sediment residual solution, and conducting testing and judgment on the washing liquid with a AgNO3 solution to ensure that Cl<-> is completely removed; and drying sediment obtained after treatment in the step 4). The BiOCl:Sm<3+> orange red fluorescent powder is prepared by a hydrolysis method. The preparation method is simple and easy, mild in conditions, economical and environmentally friendly, and suitable for large-scale production, and the prepared fluorescent powder is uniform in granularity, small in particle size, regular in shape and favorable in luminescence properties.
Description
Technical field
The present invention relates to fluorescent material and preparation method thereof, and in particular to a kind of samarium doping chlorine oxygen bismuth orange red fluorescent powder and its
Preparation method.
Background technology
Rare earth ion doped luminescent material with fluorescent material as representative is of great interest in illumination field, its
Absorbability is strong, and transformation efficiency is high, and rare earth coordinates the narrow emission of ion to be conducive to total colouring, chemical and physical features
It is stable, in modern society such as escape way Warning Mark, biological monitoring, the aspect such as medical treatment detection is received greatly to be applied.
And modern most commercial is all by fluorescent material (YAG: Ce based on LED white light sources3+) switching emission method and with ultraviolet
LED illumination RGB three-color phosphor is obtained, but strategic point is to be solved precisely due to the colour temperature for lacking efficient red color light component and causing
Height, the low problem of colour rendering index, so the efficient red and orange fluorescent powder of research and development becomes the main of present researcher
Task.
Oxyhalide has a low phonon energy, excellent chemical stability and mechanical performance, and has had halide concurrently
And be a kind of luminous host material with fine development and application prospect the characteristics of oxide.And BiOCl is the one of oxyhalide
Kind, while being also a kind of new wide bandgap semiconductor materials.It has unique electronic structure and crystal structure, can be in purple
Effectively degradable organic pollutant under outer light and simulated solar irradiation, also good catalytic performance, optical property and stable
Physico-chemical property etc., has been widely used in fields such as ferroelectric material, pigment and catalyst.
BiOCl crystal structures belong to PbFCl type tetragonal crystalline structures, and its space group is P4/nmm (No.129), symmetry
For D4h.[Cl-Bi-O-Bi-Cl] atomic layer is combined by non-strong power, and adhesion is less, and short texture causes this layer structure
It is easy to along the dissociation of [001] direction.So these [Cl-Bi-O-Bi-Cl] layers are inclined to form layer structure.Due to its uniqueness
Two-dimensional slice structure, in crystals strong polarization electric field can be formed.Sm3+Ion is weight in the research of white light LEDs luminescent material
Active ions are wanted, because electronics exists4G5/2→6H7/2On transition cause Sm3+There is extremely strong emission peak, and energy at 600nm
Level structure is simple, good luminous performance, quantum efficiency are high.Therefore when rare earth ion replaces Bi3+When occupying its lattice point in lattice,
Its surrounding environment has low-symmetry and strong polarizability.This unique crystal field energy affects rare earth ion transition speed,
And may strengthen the luminous of rare earth ion.Therefore BiOCl：Sm3+It is a kind of excellent orange red fluorescent powder suitable for white light LEDs.
Traditional BiOCl：Sm3+The preparation of orange red fluorescent powder is to use solid phase method, the simple still manufacturing cycle of the method
Long and energy consumption is big, does not meet the sustainable economic development that now society advocates.
The content of the invention
The technical problem to be solved is to provide a kind of samarium doping chlorine oxygen bismuth orange red fluorescent powder and its preparation side
Method, using Hydrolyze method BiOCl is prepared：Sm3+Orange red fluorescent powder, method is simple, mild condition, economic and environment-friendly, it is adaptable to
Large-scale production, and the MODEL OF THE PHOSPHOR PARTICLE SIZE prepared is uniform, grain size is little, regular appearance, and the fluorescent material for obtaining is sent out
Optical property is excellent.
To achieve these goals, the technical solution used in the present invention is, a kind of samarium doping chlorine oxygen bismuth orange red fluorescent powder
Preparation method, comprise the following steps：
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.010～0.030；
2) load weighted raw material is put in beaker, is dropwise slowly dropped into concentrated hydrochloric acid, be stirred during dropwise addition, until
Raw material is completely dissolved to form solution A；
3) be slowly added dropwise ammonia spirit in solution A, it is 9～10 to adjust pH value, continue to stir with magnetic stirring apparatus until
Produce white depositions；
4) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
5) by step 4) process after sediment drying.
Step 2) in concentrated hydrochloric acid solution mass concentration be 37%.
Step 2) in carried out using magnetic stirring apparatus.
Step 3) in ammonia spirit mass concentration be 25%, dropwise addition mode is to be added dropwise over.
Step 5) in drying in an oven under 60 DEG C～80 DEG C air atmospheres dry, after drying with mortar it is finely ground.
A kind of samarium doping chlorine oxygen bismuth orange red fluorescent powder, its chemical formula is BiOCl：xSm3+, wherein x=0.010～
0.030。
Compared with prior art, the present invention has following beneficial technique effect：
1) present invention prepares BiOCl using Hydrolyze method：xSm3+(x=0.010～0.030) orange red fluorescent powder, method letter
It is single easy, mild condition, economic and environment-friendly, it is adaptable to mass produce, for the preparation compared to traditional high temperature solid-state method, contracting
In the short cycle that it is prepared, energy consumption is reduced, meet the sustainable economic development of modern society's requirement, comply with the trend in epoch.
2) BiOCl that the present invention is prepared：xSm3+(x=0.010～0.030) orange red fluorescent powder is through a series of
XRD, SEM and sepectrophotofluorometer test understand that sample powder even particle size distribution is substantially at 3～5 μm, grain with analysis
Footpath size is little, regular appearance, and extremely strong orange-red light is illustrated at 594nm, provides for the efficient WLED of exploitation important
Composition.
Description of the drawings
Fig. 1 is BiOCl obtained in the embodiment of the present invention 2：0.01Sm3+The XRD of fluorescent material；
Fig. 2 is BiOCl obtained in the embodiment of the present invention 2：0.01Sm3+The SEM figures of fluorescent material；
Fig. 3 is BiOCl obtained in the embodiment of the present invention 3：0.03Sm3+The launching light spectrogram of fluorescent material；
Fig. 4 is BiOCl obtained in the embodiment of the present invention 3：0.03Sm3+The exciting light spectrogram of fluorescent material；
Specific embodiment
Hereinafter, we further do to the present invention in conjunction with specific embodiments the detailed description of.
Embodiment 1
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.01；Raw material is put in beaker, the concentrated hydrochloric acid that mass concentration is 37% is added dropwise in beaker, process is added dropwise
Used in magnetic stirring apparatus be stirred, until raw material is completely dissolved to form solution A；
2) ammonia spirit that mass concentration is 25% is dropwise slowly added dropwise in solution A and adjusts pH value to 9～10, and use magnetic
Power agitator continues to stir until producing white depositions in solution；
3) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
4) by step 3) gained precipitation be placed in baking oven under 60 DEG C～80 DEG C air atmospheres dry, ground with mortar after drying
Carefully, you can obtain BiOCl：0.01Sm3+Orange red fluorescent powder.
Embodiment 2
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.01；Raw material is put in beaker, the concentrated hydrochloric acid that mass concentration is 37% is added dropwise in beaker, process is added dropwise
Used in magnetic stirring apparatus be stirred, until raw material is completely dissolved to form solution A；
2) ammonia spirit that mass concentration is 25% is dropwise slowly added dropwise in solution A and adjusts pH value to 10, and use magnetic force
Agitator continues to stir until producing white depositions in solution；
3) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
4) by step 3) gained precipitation be placed in baking oven under 70 DEG C of air atmospheres dry, after drying with mortar it is finely ground, i.e.,
BiOCl is obtained：0.01Sm3+Orange red fluorescent powder.
Fig. 1 is BiOCl obtained in the present embodiment：0.01Sm3+The XRD of fluorescent material.It can be seen that under the method
The position of the diffraction maximum of obtained sample is basic with Tetragonal BiOCl standard cards (JCPDS NO.06-0249) with relative intensity
Equally, Sm is illustrated3+Doping does not change the structure of BiOCl, and produces without dephasign, high purity 100%.
Fig. 2 is BiOCl obtained in the present embodiment：xSm3+The SEM figures of fluorescent material.As can be seen from the figure sample powder granularity
It is evenly distributed, size is 3～5 μm, and grain size is little, regular appearance, is cube block structure of standard.
Embodiment 3
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.03；Raw material is put in beaker, the concentrated hydrochloric acid that mass concentration is 37% is added dropwise in beaker, process is added dropwise
Used in magnetic stirring apparatus be stirred, until raw material is completely dissolved to form solution A；
2) ammonia spirit that mass concentration is 25% is dropwise slowly added dropwise in solution A and adjusts pH value to 10, and use magnetic force
Agitator continues to stir until producing white depositions in solution；
3) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
4) by step 3) gained precipitation be placed in baking oven under 60 DEG C of DEG C of air atmospheres dry, after drying with mortar it is finely ground,
BiOCl is obtained：0.03Sm3+Orange red fluorescent powder.
Fig. 3 is BiOCl obtained in the present embodiment：0.03Sm3+The launching light spectrogram of fluorescent material.As can be seen from the figure have
Three characteristic peaks, respectively correspond to 561nm (4G5/2→6H5/2), 594nm (4G5/2→6H7/2) and 648nm (4G5/2→6H9/2).
Under the exciting of 405nm monitoring wavelength, sample shows strong blood orange light.
Fig. 4 is BiOCl obtained in the present embodiment：0.03Sm3+The exciting light spectrogram of fluorescent material.As can be seen from the figure it is ultraviolet
The principal character peak of excitation spectrum is gathered in 350-480nm regions, mainly due to Sm3+From lower level6H5/2It is energized into more
On high level, and the Sm under the monitoring of 594nm wavelength3+Ion can produce very strong fluorescent emission in the case where short wave ultraviolet light is excited.
Embodiment 4
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.02；Raw material is put in beaker, the concentrated hydrochloric acid that mass concentration is 37% is added dropwise in beaker, process is added dropwise
Used in magnetic stirring apparatus be stirred, until raw material is completely dissolved to form solution A；
2) ammonia spirit that mass concentration is 25% is dropwise slowly added dropwise in solution A and adjusts pH value to 9, and stirred with magnetic force
Mix device to continue to stir until producing white depositions in solution；
3) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
4) by step 3) gained precipitation be placed in baking oven under 70 DEG C of air atmospheres dry, after drying with mortar it is finely ground, i.e.,
BiOCl is obtained：0.02Sm3+Orange red fluorescent powder.
Embodiment 5
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh,
Wherein x=0.03；Raw material is put in beaker, the concentrated hydrochloric acid that mass concentration is 37% is added dropwise in beaker, process is added dropwise
Used in magnetic stirring apparatus be stirred, until raw material is completely dissolved to form solution A；
2) ammonia spirit that mass concentration is 25% is dropwise slowly added dropwise in solution A and adjusts pH value to 9, and stirred with magnetic force
Mix device to continue to stir until producing white depositions in solution；
3) by white depositions centrifugation, deionized water is repeatedly washed in removal white depositions residual solution
Cl—, and use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
4) by step 3) gained precipitation be placed in baking oven under 80 DEG C of air atmospheres dry, after drying with mortar it is finely ground, i.e.,
BiOCl is obtained：0.03Sm3+Orange red fluorescent powder.
Claims (6)
1. a kind of preparation method of samarium doping chlorine oxygen bismuth orange red fluorescent powder, it is characterised in that comprise the following steps：
1) with Sm2O3And Bi2O3As raw material, according to chemical formula BiOCl：xSm3+Stoichiometric proportion carry out raw material and weigh, wherein
X=0.010～0.030；
2) load weighted raw material is put in beaker, is dropwise slowly dropped into concentrated hydrochloric acid, be stirred during dropwise addition, until raw material
It is completely dissolved to form solution A；
3) ammonia spirit is slowly added dropwise in solution A, it is 9～10 to adjust pH value, continues to stir with magnetic stirring apparatus until producing
White depositions；
4) by white depositions centrifugation, deionized water repeatedly washs the Cl removed in white depositions residual solution—, and
Use AgNO3Solution is tested judgement to cleaning solution, to guarantee Cl—Remove completely；
5) by step 4) process after sediment drying.
2. a kind of preparation method of samarium doping chlorine oxygen bismuth orange red fluorescent powder according to claim 1, it is characterised in that step
It is rapid 2) in concentrated hydrochloric acid solution mass concentration be 37%.
3. a kind of preparation method of samarium doping chlorine oxygen bismuth orange red fluorescent powder according to claim 1, it is characterised in that step
It is rapid 2) in carried out using magnetic stirring apparatus.
4. a kind of preparation method of samarium doping chlorine oxygen bismuth orange red fluorescent powder according to claim 1, it is characterised in that step
It is rapid 3) in ammonia spirit mass concentration be 25%, dropwise addition mode is to be added dropwise over.
5. a kind of preparation method of samarium doping chlorine oxygen bismuth orange red fluorescent powder according to claim 1, it is characterised in that step
Rapid 5) middle drying is the drying under 60 DEG C～80 DEG C air atmospheres in an oven, finely ground with mortar after drying.
6. a kind of samarium doping chlorine oxygen bismuth orange red fluorescent powder, it is characterised in that its chemical formula is BiOCl：xSm3+, wherein x=
0.010～0.030.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06128564A (en) * | 1992-10-14 | 1994-05-10 | Fuji Photo Film Co Ltd | Bismuth oxyhalide phosphor and radiation-sensitized screen |
| CN1513943A (en) * | 2003-07-02 | 2004-07-21 | 中国科学院上海硅酸盐研究所 | Preparation method of nano-level yttrium oxide base luminous powder doped with rare earth |
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611264878.1A patent/CN106635002A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06128564A (en) * | 1992-10-14 | 1994-05-10 | Fuji Photo Film Co Ltd | Bismuth oxyhalide phosphor and radiation-sensitized screen |
| CN1513943A (en) * | 2003-07-02 | 2004-07-21 | 中国科学院上海硅酸盐研究所 | Preparation method of nano-level yttrium oxide base luminous powder doped with rare earth |
| CN103421511A (en) * | 2013-08-30 | 2013-12-04 | 昆明理工大学 | Bismuth oxyhalide light-emitting material with doped rare earth ions and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 20150115: "稀土掺杂BiOCl的Stocks及反Stocks特异性发光研究", 《昆明理工大学硕士学位论文》 * |
| YANG-YANG GUO等: "Synthesis of three-dimensional flower-like BiOCl:RE3+(RE3+= Eu3+,Sm3+) globular microarchitectures and their luminescence properties", 《APPLIED SURFACE SCIENCE》 * |
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Application publication date: 20170510 |